Herbicidal 2-(hectero)aryloxy-6-arypyridines and 2-aryl-4-(hetero)aryloxypyrimidines

ABSTRACT

New herbicidal pyridine and pyrimidine derivatives of general formula (I),    &lt;IMAGE&gt;  (I)  wherein Z represents a nitrogen atom or a C-H group; A represents an optionally substituted aryl group or an optionally substituted 5- or 6-membered nitrogen-containing heteroaromatic group; n represents an integer from 0 to 2 and R1 or each R1 independently represents a hydrogen atom or an optionally substituted alkyl, alkoxy, alkylthio or dialkylamino group; m represents an integer from 0 to 5 and R2 or each R2 independently represents a hydrogen or a halogen atom or an optionally substituted alkyl, haloalkyl, haloalkoxy, alkoxy, alkylthio group or a nitro, cyano or a halosulphonyl group; and X represents an oxygen or sulphur atom.

This is a continuation of application Ser. No. 08/454,044 filed on May 30, 1995, now abandoned.

The present invention relates to certain 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines, their preparation and use as herbicides.

Pyridines, pyrimidines and their derivatives have many uses in the pharmaceutical area as well as in agriculture (herbicides, fungicides, acaricides, anthelmintics, bird repellents), reagents, intermediates and chemicals for the polymer and textile industry.

2-Arylpyrimidines and 2-pyrimidinyl-6-arylpyridines for example have been described as fungicides (DE 40 29 654 and JO 2131-480, respectively). EP 263 958 is concerned with herbicidal 2,6-diphenylpyridines, and structurally related 2,4-diphenylpyrimidines have been disclosed in EP 354,766 and 425,247, respectively, which are also said to be herbicides. Another example are 2,6-diphenoxypyridines, which have been published in EP 572,093 as herbicides. 4-Phenoxy-2-pyrazol-1-yl-pyrimidines are disclosed in DE 29 35 578 to have fungicidal activity. Huelsen (Diplomarbeit, Konstanz 1993) describes four distinct 2-(1-methyl-3-trifluoromethylpyrazol-5-ylyoxy)-6-phenyl pyridines, however, no biological activity is disclosed.

Surprisingly, it has now been found that good herbicidal activity is present in related, novel pyridine and pyrimidine derivatives having both an aryl group and an aryloxy or a heteroaryloxy group. These compounds unexpectedly show excellent activity and good crop selectivity in pre- and post-emergence applications on both broadleaf and grassy weed species.

Accordingly, the present invention provides 2,6-substituted pyridines and 2,4-substituted pyrimidines of the general formula I ##STR2## wherein Z represents a nitrogen atom or a C--H group; A represents an optionally substituted aryl group or an optionally substituted 5- or 6-membered nitrogen-containing heteroaromatic group; n represents an integer from 0 to 2 and R¹ or each R¹ independently represents a hydrogen atom or an optionally substituted alkyl, alkoxy, alkylthio or dialkylamino group; m represents an integer from 0 to 5 and R² or each R² independently represents a hydrogen or a halogen atom or an optionally substituted alkyl, haloalkyl, haloalkoxy, alkoxy, alkylthio group or a nitro, cyano or a halosulphonyl group; and X represents an oxygen or sulphur atom; with the proviso that when Z is C--H, A is 1-methyl-3 trifluoromethyl-pyrazol-5-yl, n is 0 and X is oxygen, then m must be other than 0 and when m is 1 then R² cannot be a 3-trifluoromethyl substituent and when m is 2, then R² cannot be a 2,4-dichloro substituent or a 2,4 dimethyl substituent.

An aryl group as substituent or part of other substituents is suitably an optionally substituted phenyl or naphthyl group. A 5- or 6-membered heteroaryl group comprises optionally substituted 5- or 6 membered heterocycles containing one or more nitrogen and/or oxygen and/or sulfur atoms, 1 to 3 nitrogen atoms being preferred. Example of such groups are pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyridazinyl and triazinyl groups.

Generally, when any of the above mentioned moieties comprises an alkyl group, this alkyl group, unless otherwise specified, may be linear or a branched and may suitably contain 1 to 12, preferably 1 to 4, carbon atoms. Examples of such groups are methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl and tertiary-butyl groups. An alkyl portion of a haloalkyl, haloalkoxy, alkylthio or alkoxy group suitably has from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms.

Halogen represents a fluorine, chlorine, bromine or iodine atom. Haloalkyl and haloalkoxy are preferably mono-, di- or trifluoroalkyl and -alkoxy, especially trifluoromethyl and trifluoromethoxy.

When any groups are designated as being optionally substituted, the substituent groups which are optionally present may be any of those customarily employed in the modification and/or development of pesticidal compounds and are especially substituents that maintain or enhance the herbicidal activity associated with the compounds of the present invention, or influence persistence of action, soil or plant penetration, or any other desirable property of such herbicidal compounds. There may be one or more of the same or different substituents present in each part of the molecules. In relation to moieties defined above as comprising an optionally substituted alkyl group, including alkyl parts of haloalkyl, alkoxy, alkylthio haloalkoxy and dialkylamino groups, specific examples of such substituents include phenyl, nitro, cyano, hydroxyl, C₁₋₄ -alkoxy, C₁₋₄ -haloalkoxy and C₁₋₄ -alkoxycarbonyl groups.

In relation to moieties defined above as comprising an optionally substituted aryl or heteroaryl group, optional substituents include halogen, especially fluorine, chlorine and bromine and nitro, cyano, amino, hydroxyl, C₁₋₄ -alkyl, C₁₋₄ -alkoxy, C₁₋₄ -haloalkyl, C₁₋₄ -haloalkoxy and halosulphonyl groups. 1 to 5 substituents may suitably be employed, 1 to 2 substituents being preferred.

The compounds according to general formula I are oils, gums, or, predominantly, crystalline solid materials. They can be used in agriculture or related fields for the control of undesired plants such as Alopecurus myosuroides, Echinochloa crus-galli, Setaria viridis, Galium aparine, Stellaria media, Veronica persica, Lamium purpureum, Viola arvensis, Abutilon theophrasti, lpomoea pur-purea and Amaranthus retroflexus by pre- and post-emergence application. The compounds of general formula I according to the invention possess a high herbicidal activity within a wide concentration range and may be used in agriculture without any difficulties.

Preferred compounds are those wherein A represents a phenyl, pyridyl, or pyrazolyl group, being substituted by one or more identical or different substituents selected from halogen atoms, alkyl, alkoxy, haloalkyl, haloalkoxy and pentahalosulphonyl groups.

Especially preferred are compounds bearing a substituent in group A in meta-position relative to the point of attachment of this group.

Good results in terms of control of undesired plant growth are obtained when A is meta-substituted by a chlorine atom or a trifluoromethyl group, especially A being a 2-chloropyrid-4-yl, 1-methyl-3-trifluoromethylpyrazol-5-yl or 3-trifluoromethylphenyl group.

Particularly good results in control of weeds are achieved with compounds wherein X represents an oxygen atom.

Especially good results are obtained with compounds wherein Z represents a nitrogen atom.

Among the compounds exemplified by the invention are the following compounds:

2-(1'-methyl-3'-trifluoromethylpyrazol-5'-yloxy)-6-(4"-trifluoromethylphenyl)pyridine,

2-(2',4'-difluorophenyl)-6-methyl-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine,

2-(2',4'-difluorophenyl)-6-methyl-4-(3"-trifluoromethylphenoxy)pyrimidine,

2-(2'-chloropyrid-4'-yloxy)-(4"-trifluoromethylphenyl)pyridine,

2-(2'-chloropyrid-4'-yloxy)-6-(3"-trifluoromethylphenyl)pyridine,

2-(3'-chlorophenyl)-5-methyl-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine,

2-(3'-chlorophenyl)-5-methyl-4-(3"-trifluoromethylphenoxy)pyrimidine,

2-(4'-fluorophenyl)-6-methyl -4-(3"-trifluoromethylphenoxy)pyrimidine,

2-(4'-fluorophenyl)-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)-5-methylpyrimidine,

2-(4'-fluorophenyl)4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)-6-methyl-pyrimidine,

4-(2"-chloropyrid-4"-yloxy)-2-(2',4'-difluorophenyl)-5-methylpyrimidine,

4-(2"-chloropyrid-4"-yloxy)-5,6-dimethyl-2-(4'-trifluoromethoxyphenyl)pyrimidine,

4-(2"-chloropyrid-4"-yloxy)-5,6-dimethyl-2-(4'-trifluoromethylphenyl)pyrimidine,

4-(2"-chloropyrid-4"-yloxy)-5-methyl-2-(4'-trifluoromethoxyphenyl)pyrimidine,

4-(2"-chloropyrid-4"-yloxy)-5-methyl-2-(4'-trifluoromethylphenyl)pyrimidine

4-(2'-chloropyrid-4"-yloxy)-6-methyl-2-(4'-trifluoromethoxyphenyl)pyrimidine,

4-(2"-chloropyrid-4"-yloxy)-6-methyl-2-(4'-trifluoromethylphenyl)pyrimidine

4-methyl-6-(4"-trifluoromethoxyphenyl)-2-(1'-methyl-3'-trifluoromethylpyrazol-5'-yloxy)pyridine,

4-methyl-6-(4"-trifluoromethoxyphenyl)-2-(2'-chloropyrid-4'-yloxy)pyridine,

4-methyl-6-(4"-trifluoromethoxyphenyl)-2-(2'-chloropyrid-4'-yloxy)pyridine,

4-methyl-6-(4"-trifluoromethylphenyl)-2-(1'-methyl-3'-trifluoromethylpyrazol-5'-yloxy)pyridine,

4-methyl-6-(4"-trifluoromethylphenyl)-2-(2'-chloropyrid-4'-yloxy)pyridine,

5,6-dimethyl-2-(4'-trifluoromethoxyphenyl)-2-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine,

5,6-dimethyl-2-(4'-trifluoromethoxyphenyl)-4-(3"-trifluoromethylphenoxy)pyrimidine,

5,6-dimethyl-2-(4'-trifluoromethylphenyl)-4-(3"-trifluoromethylphenoxy)pyrimidine,

5,6-dimethyl-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)-2-(4'-trifluoromethylphenyl)pyrimidine,

5-methyl-2-(3'-methylphenyl)-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine,

5-methyl-2-(3'-methylphenyl)-4-(3"-trifluoromethylphenoxy)pyrimidine,

5-methyl-2-(4'-trifluoromethoxyphenyl)-2-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine,

5-methyl-2-(4'-trifluoromethoxyphenyl)-4-(3"-trifluoromethylphenoxy)pyrimidine,

5-methyl-2-(4'-trifluoromethylphenyl)-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine,

5-methyl-4-(3"-trifluoromethylphenoxy)-2-(4'-trifluoromethylphenoxy)pyrimidine,

6-(4"-fluorophenyl)-2-(1'-methyl-3'-trifluoromethylpyrazol-5'-yloxy)pyridine,

6-methyl-2-(4'-trifluoromethoxyphenyl)-2-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine,

6-methyl-2-(4'-trifluoromethoxyphenyl)-4-(3"-trifluoromethylphenoxy)pyrimidine,

6-methyl-4-(3"-trifluoromethylphenoxy)-2-(4'-trifluoromethylphenyl)pyrimidine, and the like.

The present invention also provides a process for the preparation of a compound of general formula I, which comprises the reaction of a compound of general formula III ##STR3## with a compound of general formula IV ##STR4## wherein Z, A, R¹, R², m, n and X are as defined hereinbefore; Hal represents a halogen atom; and M represents a metal atom.

The halogen atom Hal may be any halogen atom, suitably a fluorine, chlorine or bromine atom. The metal atom M may be any metal atom, suitably an alkali metal atom such as sodium and potassium.

In practice, the reaction may be carried out in the absence or presence of a solvent which promotes the reaction or at least does not interfere with it. Preferred are polar, aprotic solvents, suitably being N,N-dimethylformamide or dimethylsulfoxide or sulfolane or an ether, such as tetrahydrofurane or dioxane, or mixtures thereof. The reaction is carried out at a temperature between ambient temperature and the reflux temperature of the reaction mixture, preferably at elevated temperature, especially reflux temperature.

Compounds of formula III in which Z is C--H and n is 0 may be obtained by reacting a compound of general formula V ##STR5## wherein R² and m are as defined hereinbefore, with an aldehyde, suitably formaldehyde, and a dialkylamine, suitably dimethylamine, according to Org. Synthesis Col. Vol III, 305f, in a solvent, conveniently an alcohol, preferably ethanol, to give a compound of general formula VI, ##STR6## which is subsequently reacted according to DBP 21 47 288 (1971) with an ammonium salt, suitably ammonium acetate, and a compound of general formula VII, ##STR7## wherein Y is an alkoxy group or an NH₂ -group, preferably an ethoxy group, in a solvent, suitably an alcohol, preferably ethanol, to give a compound of general formula VIII, ##STR8## which is further converted by reacting VIII with phosphoryl halogenides (Muller, E., Chem. Ber. 42. 423 (1909); Katritzky et al., J. Chem. Soc., Perkin Trans. Part 1, 1980, 2743-2754), preferably phosphoryl bromide or phosphoryl chloride at elevated temperatures, ideally reflux temperature, to give a compound of general formula III.

An alternative, and preferred process for the preparation of compounds of general formula III in which Z is C--H, comprises reacting a 2,6-dihalopyridine of general formula IX ##STR9## wherein R¹ and n are as defined hereinbefore, and each Hall and Hal₂ independently represents a halogen atom, with an in situ prepared metalated benzene derivative of general formula (X) in an approximately equimolar ratio, ##STR10## wherein R² and m are as defined hereinbefore, and M represents an alkali metal atom.

The alkali metal may be any alkali metal, preferably lithium, and the reaction may be carried out in an aprotic, polar solvent, preferably ethers, to give a compound of general formula III, essentially as disclosed in Cook and Wakefield, J. Chem. Soc., 1969, 2376.

A process for the preparation of compounds of formula III, in which Z represents a nitrogen atom, comprises the reaction of benzamidine hydrochlorides of the general formula XI ##STR11## wherein R² and m are as defined hereinbefore with a compound of formula XII, ##STR12## wherein each R¹ ₁ and R¹ ₂ independently are as defined hereinbefore; and the O-alkyl group is suitably methoxy or ethoxy, to give a pyrimidinone of general formula XIII. ##STR13##

Compounds of general formula XI are known or may be prepared according to procedures described in the art, for example in Tetrahedron, 33, 1675f (1979) and J. Org. Chem., 26, 412f. (1960).

The reaction of compounds of formulae XI and XII may be carried out according to Liebigs Ann. 1980, 1392f in an organic solvent, suitably an alcohol and preferably ethanol, and in the presence of a base, suitably metal alkoxides, preferably sodium ethoxide.

Compounds of formula XII may subsequently be converted into compounds of formula III, essentially as described in Davies and Pigott, J. Chem. Soc., 1945, 347, by reaction with a phosphoryl halogenide or thionyl halogenide, preferably phosphoryl chloride, ideally in the absence of a solvent, at elevated temperatures to obtain compounds of formula III.

Compounds of general formula IV are known or may be prepared by known methods. They may be prepared and isolated separately or may be prepared in situ. Generally, a compound of general formula XIV ##STR14## wherein A and X are as hereinbefore defined is reacted with a suitable metal base, for example a metal carbonate or hydride. Preferably the metal salt is a sodium or potassium salt.

Compounds of general formula I may, if desired, be isolated and purified using conventional techniques.

The present invention also provides the use of a compound of general formula I as a herbicide. Further, in accordance with the invention there is provided a method of combating undesired plant growth at a locus by treating the locus with a composition according to the invention or a compound of formula I. The treatment may be a foliar spray application, the locus is most suitably the plants in a crop area, typical crops being cereals, maize, soya bean, sunflower or cotton. However, application may also be to the soil for those compounds having pre-emergence herbicidal action. The dosage of active ingredient used may, for example be in the range of from 0.01 to 10 kg/ha, preferably 0.1 to 1 kg/ha.

The present invention also provides a herbicidal composition which comprises a compound of formula I and at least one carrier.

Preferably there are at least two carriers in a composition of the present invention, at least one of which is a surface-active agent.

A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may be, as appropriate, a plant, seed or soil, or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including a material which is normally gaseous but which has been compressed to form a liquid, and any of the carriers normally used in formulating herbicidal compositions may be used. Preferably compositions according to the invention contain 0.5 to 95% by weight of active ingredient.

Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicates such as diatomaceous earths; magnesium silicates, for example talcs; magnesium aluminium silicates, for example attapulgites and vermiculites; aluminium silicates, for example kaolinites, montmorillonites and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates; elements, for example carbon and sulphur; natural and synthetic resins, for example coumaron resins, polyvinyl chloride, and styrene polymers and copolymers; solid polychlorophenols, bitumen; waxes; solid fertilisers, for example superphosphates.

Suitable liquid carriers include water; alcohols, for example isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic or araliphatic hydrocarbons, for example benzene, toluene and xylene; petroleum fractions, for example kerosene and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene and trichloroethane. Mixtures of different liquids are often suitable.

Agricultural compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surface-active agent facilitates this process of dilution. Thus preferably at least one carrier in a composition according to the invention is a surface active agent. For example, the composition may contain at least two carriers, at least one of which is a surface-active agent.

A surface-active agent may be an emulsifying agent, a dispersing agent or a wetting agent; it may be non-ionic or ionic, examples of suitable surface-active agents include the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitol, sucrose or pentaerythrol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols, for example p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or earth alkali metal salts, preferably sodium salts, or sulphuric or sulphonic acid esters containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates such as dodecylbenzene sulphonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The herbicidal composition of the invention may also contain other active ingredients, for example, compounds possessing insecticidal or fungicidal properties, or other herbicides.

The following examples illustrate the invention. The structures of the compounds prepared in the following examples were additionally confirmed by NMR and mass spectrometry.

EXAMPLES Example 1 β-Dimethylamino propiophenone hydrochloride

Acetophenone (29.1 ml, 0.25 mol), para-formaldehyde (12.0 g, 0.40 mol) and dimethyl amine hydrochloride (28.5 g, 0.35 mol) are suspended in ethanol (50 ml). Concentrated hydrochloric acid (0.5 ml) is added and the mixture is heated to reflux for 4 h. Then acetone (200 ml) is added and the resulting clear solution is allowed to cool to ambient temperature. The precipitate is collected by filtration and crystallized from ethanol yielding the title compound (40.7 g, 76.0% of theoretical yield) as colorless crystals with mp. 158° C.

Examples 2-4

Additional examples of general formula VI are prepared as exemplified by Example 1. Details are given in Table I

                  TABLE I                                                          ______________________________________                                          ##STR15##                                                                     Ex.                      mp     yield                                          No.    R.sup.2           (°C.)                                                                          (%)                                            ______________________________________                                         2      3-trifluoromethyl 157    63                                             3      2,4-dichloro      136    51                                             4      2,4-dimethyl      134    72                                             ______________________________________                                    

Example 5 6-Phenyl-2-pyridone

Ethyl 2-chloroacetate (10.6 ml, 0.1 mol) is slowly added to hot (105° C.) pyridine (8.9 ml, 0.11 mmol whereby the temperature is maintained in the range of 100° C. to 110° C. The resulting brown oil is dissolve in ethanol (60 ml), β-dimethylamino propiophenone hydrochloride (17.7 g, 0.1 mol; prepared to according to Example 1) and ammonium acetate (60 g) are added and the mixture is boiled under reflux for 4 h. After cooling, the mixture is filtered and the solvent is evaporated in vacuo. The residue is crystallized from water, collected by filtration and purified by re-crystallization from toluene. The title compound is obtained as colorless crystals (4.7 g, 28% of th.) with mp 200° C.

Example 6-8

Additional examples are analogously prepared to Example 5. Details are given in Table II.

                  TABLE II                                                         ______________________________________                                          ##STR16##                                                                     Ex.                      mp     yield                                          No.    R.sup.2           (°C.)                                                                          (%)                                            ______________________________________                                         6      3-trifluoromethyl 174    36                                             7      2,4-dichloro      255    56                                             8      2,4-dimethyl      209    23                                             ______________________________________                                    

Example 9 2-Bromo-6-phenyl pyridine

A mixture of 6-phenyl pyridone (3 g, 17.5 mmol; prepared according to Example 6) and phosphoryl bromide (7.2 g, 25.0 mmol) is heated to 100° C. for 5 h. The cooled mixture is poured into water (40 ml) and the pH is adjusted to 9 by addition of saturated aqueous sodium carbonate. Then the layers are separated and the aqueous layer is extracted with ethyl acetate (50 ml). The combined organic layers are dried with anhydrous magnesium sulphate and the solvent is evaporated in vacuo. The crude product is crystallized from aqueous ethanol. Subsequent purification by flash chromatography (silica gel, hexane/ethyl acetate 9/1 v/v) gives 2-bromo-6-phenyl pyridine (3.1 g, 76% of th.) as light brown crystals with mp 50° C.

Examples 10-12

Additional compounds of general formula III are prepared by procedures analogous to that of Example 9. Details are given in Table III.

                  TABLE III                                                        ______________________________________                                          ##STR17##                                                                     Ex.                      mp     yield                                          No.    R.sup.2           (°C.)                                                                          (%)                                            ______________________________________                                         10     3-trifluoromethyl oil    82                                             11     2,4-dichloro      123    88                                             12     2,4-dimethyl      oil    68                                             ______________________________________                                    

Example 13 2-(1'-Methyl-3'-trifluoromethyl pyrazol-5'-yloxy) 6-phenyl pyridine

A mixture of 2-bromo-6-phenyl pyridine (0.5 g, 2.1 mmol; prepared according to Example 9), 1-methyl-3-fluoromethyl-5-hydroxypyrazole (0.65 g, 3.9 mmol), potassium carbonate (0.6 g, 4.3 mmol) and N,N-dimethyl formamide (2 ml) are heated to reflux for 12 h. Then the reaction mixture is directly applied onto a flash chromatography column (silica gel). Elution with hexane/ethyl acetate (9/1 v/v) gives the title compound (0.35 g, 52.0% of th.) as light-yellow oil.

Examples 14-16

The compounds specified in Table 4 are obtained by procedures analogous to that of Example 13.

                  TABLE IV                                                         ______________________________________                                          ##STR18##                                                                     Ex.                               mp   yield                                   No.   A               R.sup.2     (°C.)                                                                        (%)                                     ______________________________________                                         14    1'-CH.sub.3 -3'-CF.sub.3 -pyrazol-5'-yl                                                        3"-CF.sub.3 113  93                                      15    1'-CH.sub.3 -3'-CF.sub.3 -pyrazol-5'-yl                                                        2",4"-dichloro                                                                              91  78                                      16    1'-CH.sub.3 -3'-CF.sub.3 -pyrazol-5'-yl                                                        2",4"-dimethyl                                                                             oil  95                                      ______________________________________                                    

Example 17 2-Fluoro-6-(4'-fluorophenyl)-pyridine

Butyl lithium (105.0 ml, 0.26 mol, 2.5M solution in hexane) is added to a solution of 1-bromo-4-fluoro benzene (34. 3 ml, 0.31 mol) in anhydrous diethyl ether (200 ml) at -20° C. The mixture is stirred for 60 min and then chilled to -40° C. 2,6-Difluoropyridine (22.7 ml, 0.25 mol) is added and the reaction mixture is allowed to warm to ambient temperature. Subsequently, the mixture is washed with saturated aqueous ammonium chloride (300 ml). The layers are separated and the aqueous layer is washed with diethyl ether 3 times (100 ml each). After drying of the combined organic layers with anhydrous magnesium sulphate, the solvent is removed in vacuo. The crude product is purified by flash column chromatography (silica gel, hexane/AcOEt 8/2) yielding colorless crystals of 2-fluoro-6-(4'-fluorophenyl)-pyridine (19.8 g, 41.0% of th.) with mp 34° C.

Examples 18-19

Analogously to Example 17, the examples of general formula III are prepared as specified in Table V.

                  TABLE V                                                          ______________________________________                                          ##STR19##                                                                     Ex.                            mp   yield                                      No.      R.sup.1                                                                              R.sup.2         (°C.)                                                                        (%)                                        ______________________________________                                         18       --    --              oil  47                                         19       --    4'-trifluoromethyl                                                                             58   75                                         20       --    3'-trifluoromethyl                                                                             oil  72                                         ______________________________________                                    

Example 21 2-(3'-Chlorpyrid-5'-yloxy)-6-(4"-fluorophenyloxy)-pyridine

A mixture of 2-fluoro-6-(4'-fluorophenyl)-pyridine (1.9 g, 10.0 mmol, prepared according to Example 17), 3-chloro-5-hydroxpyridine (1.4 g, 11.0 mmol) and potassium carbonate (1.5 g, 11.0 mmol) in sulfolane (10 ml) is heated to reflux for 8 h. The mixture is allowed to cool to ambient temperature and is then filtered through a bed of silica gel which is subsequently washed with ethyl acetate. The organic solutions are combined and the solvent is evaporated in vacuo. The remaining material is applied onto the top of a flash chromatography column (silica gel) and eluted with hexane/ethyl acetate. Elution with hexane/ethyl acetate (8/2 v/v) gives 2-(3'-chlorpyrid-5'-yloxy)-6-(4"-fluorophenyloxy)-pyridine (1.4g, 46% of th.) as light brown crystals with mp 139° C.

Examples 22-30

Additional compounds are prepared analogously to Example 21. Details are found in Table VI.

                  TABLE VI                                                         ______________________________________                                          ##STR20##                                                                     Ex.                                  mp   yield                                No.  R.sup.1                                                                              A               R.sup.2   (°C.)                                                                        (%)                                  ______________________________________                                         22   --    3'-CF.sub.3 -phenyl                                                                            4"-fluoro oil  48                                   23   --    2'-chloropyrid-4'-yl                                                                           4"-fluoro 137  37                                   24   --    2'-chloropyrid-4'-yl                                                                           --        109  35                                   25   --    2'-chloropyrid-4'-yl                                                                           4"-trifluoromethyl                                                                       105  51                                   26   --    1'-CH.sub.3 -3'-CF.sub.3 -pyrazol-5'-yl                                                        4"-fluoro  87  44                                   27   --    1'-CH.sub.3 -3'-CF.sub.3 -pyrazol-5'-yl                                                        4"-trifluoromethyl                                                                        94  59                                   28   --    1'-CH.sub.3 -3'-CF.sub.3 -pyrazol-5'-yl                                                        3"-trifluoromethyl                                                                       112  44                                   29   --    2'-chloropyrid-4'-yl                                                                           3"-trifluoromethyl                                                                        92  54                                   30   --    2',4'-difluorophenyl                                                                           3"-trifluoromethyl                                                                       oil  72                                   ______________________________________                                    

Example 31 4-Fluorobenzamidine

4-Fluorobenzonitrile (10 g, 83 mmol) is dissolved in a mixture of anhydrous ethanol (5 ml) and diethyl ether (70 ml). The reaction mixture is cooled to ice-bath temperature and saturated with gaseous hydrogen chloride for 90 minutes. The mixture is allowed to warm to ambient temperature and stirred overnight.

The colorless precipitates are filtered off, washed with diethyl ether and dissolved in anhydrous ethanol (20 ml). Diethyl ether (100 ml) saturated with gaseous ammonia is added and stirred for 3 hours.

The resulting suspension is filtered and the solvent of the filtrate is removed in vacuo. The residue is washed with diisopropyl ether. After drying colorless crystals (5.15g, 35.5%) of melting point 210° C. are obtained.

Example 32 to 37

By methods analogous to that of example 31, further compounds of the general formula XI in table VII.

                  TABLE VII                                                        ______________________________________                                          ##STR21##                                                                     Ex.                      mp     yield                                          No.    R.sup.2           (°C.)                                                                          (%)                                            ______________________________________                                         32     4-trifluoromethyl 167    21.4                                           33     3-methyl          243    29.7                                           34     3-chloro          148    17.5                                           35     3,4-difluoro      185    17.4                                           36     3-trifluoromethyl 181    17.6                                           37     3-fluoro          143    20.0                                           ______________________________________                                    

Example 38 2-(4-'-Fluorophenyl)-5-methyl-4-pyrimidinone

Sodium hydride (0.52 g, 13 mmol) is added to 20 ml of anhydrous ethanol and stirred for 30 minutes at ambient temperature. To this, 4-fluorobenzamidine hydrochloride (1.47 g, 8.5 mmol) (from example 1) is added and the mixture is stirred for further 30 minutes. Methyl 2-formylpropionate (1 g, 10.6 mmol) is added dropwise and the reaction mixture is left for 4 days under stirring at ambient temperature.

After cooling, the solvent is removed in vacuo and the residue is dissolved in aqueous sodium hydroxide (10 ml, 1M). Then the mixture is brought to pH 5 with 2 molar hydrochloric acid. The precipitate is filtered off and washed with diisopropyl ether. After drying, colorless crystals (0.44 g, 10.3%) of melting point >250° C. are obtained.

Examples 39 to 55

By the method examplified in example 38, further compounds of the general formula III are prepared. Details are given table VIII.

                  TABLE VIII                                                       ______________________________________                                          ##STR22##                                                                     Ex.                            mp    yield                                     No.    R.sup.1   R.sup.2       (°C.)                                                                         (%)                                       ______________________________________                                         39     6-methyl  4'-fluoro     267   56.8                                      40     5-methyl  4'-trifluoromethyl                                                                           >250  58.7                                      41     6-methyl  4'-trifluoromethyl                                                                           209   82.2                                      42     5-methyl  3'-methyl     169   34.3                                      43     6-methyl  3'-methyl     185   41.6                                      44     5-methyl  3'-chloro     260   61.4                                      45     6-methyl  3'-chloro     218   51.0                                      46     5-methyl  3',4'-difluoro                                                                               >250  59.4                                      47     6-methyl  3',4'-difluoro                                                                               225   51.3                                      48     5-methyl  3'-trifluoromethyl                                                                           204   39.8                                      49     6-methyl  3'-trifluoromethyl                                                                           109   26.6                                      50     5,6-dimethyl                                                                             3'-trifluoromethyl                                                                           215   70.4                                      51     5,6-dimethyl                                                                             4'-trifluoromethyl                                                                           242   63.5                                      52     5-methyl  4'-chloro     >250  27.2                                      53     6-methyl  4'-chloro     227    6.8                                      54     5-methyl  3'-fluoro     238   56.0                                      55     6-methyl  3'-fluoro     194   48.4                                      ______________________________________                                    

Example 56 2-(4'-Fluorophenyl)-4-chloro-5-methylpyrimidine

A mixture of 2-(4'-fluorophenyl)-5-methyl-4-pyrimidinone (0.79 g, 3.9 mmol) (from example 5) and phosphorous oxychloride (3 ml) is heated to reflux for 1 hour.

The main excess of phosphorous oxychloride is removed in vacuo and the residue is quenched with water (10 ml) to hydrolyze the remaining reagent. The mixture is neutralized and then extracted with ethyl acetate (50 ml). After drying of the organic layer with anhydrous magnesium sulphate, the solvent is removed in vacuo. The title compound (0.63 g, 72.6%) is obtained as colorless crystals of melting point 133°.

Example 57-73

The compounds of general formula (XIII) listed in table IX are prepared analogously to the method of example 56.

                  TABLE IX                                                         ______________________________________                                          ##STR23##                                                                     Ex.                             mp   yield                                     No.    R.sup.1     R.sup.2      (°C.)                                                                        (%)                                       ______________________________________                                         57     6-methyl    4'-fluoro    143  97.0                                      58     6-methyl    4'-trifluoromethyl                                                                          62   71.8                                      59     5-methyl    4'-trifluoromethyl                                                                          109  87.3                                      60     5-methyl    3'-methyl    154  98.8                                      61     6-methyl    3'-methyl    134  73.7                                      62     5-methyl    3'-chloro    87   94.1                                      63     6-methyl    3'-chloro    101  26.1                                      64     5-methyl    3',4'-difluoro                                                                              114  92.0                                      65     6-methyl    3',4'-difluoro                                                                              94   90.7                                      66     5,6-dimethyl                                                                               3'-trifluoromethyl                                                                          83   81.6                                      67     5,6-dimethyl                                                                               4'-trifluoromethyl                                                                          57   54.5                                      68     5-methyl    3'-trifluoromethyl                                                                          101  81.4                                      69     6-methyl    3'-trifluoromethyl                                                                          62   87.3                                      70     5-methyl    4'-chloro    162  85.2                                      71     6-methyl    4'-chloro    101  83.6                                      72     5-methyl    3'-fluoro    95   83.7                                      73     6-methyl    3'-fluoro    86   71.5                                      ______________________________________                                    

Example 74 2-(4'-Fluorophenyl)-4-(3"-trifluoromethylphenoxy)-6-methylpyrimidine

A mixture of 2-(4'-fluorophenyl)-4-chloro-6-methylpyridine (0.6 g, 2.7 mmol) (from example 14), α,α,α-3-hydroxybenzotrifluoride (0.49 g, 3 mmol) and potassium carbonate (0.41 g, 3 mmol) in N,N-dimethylformamide (3 ml) is heated to reflux for 2 hours.

After cooling, ethyl acetate (10 ml) is added and the suspension is filtered through a bed of silica gel using ethyl acetate. The solvent of the filtrate is removed in vacuo and the residue purified by flash silica gel column chromatography using hexane/ethyl acetate 7/2.

Removal of the solvent affords colourless crystals (0.53g, 56.4%) of melting point 58° C.

Example 75-97

Further compounds of the general formula I are prepared by the procedure of example 74. Details are given in table X.

                                      TABLE X                                      __________________________________________________________________________      ##STR24##                                                                     Ex.                             mp  yield                                      No. R.sup.1                                                                              R.sup.2                                                                               A              (°C.)                                                                       (%)                                        __________________________________________________________________________     75  5-methyl                                                                             4'-fluoro                                                                             1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    133 54.7                                       76  6-methyl                                                                             4'-fluoro                                                                             3"-CF.sub.3 -phenoxy                                                                          123 21.0                                       77  6-methyl                                                                             4'-CF.sub.3                                                                           1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    98  39.5                                       78  6-methyl                                                                             4'-CF.sub.3                                                                           3"-CF.sub.3 -phenoxy                                                                          89  79.9                                       79  5-methyl                                                                             4'-CF.sub.3                                                                           1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    147 27.6                                       80  5-methyl                                                                             4'-CF.sub.3                                                                           3"-CF.sub.3 -phenoxy                                                                          95  97.6                                       81  5-methyl                                                                             3'-CH.sub.3                                                                           1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    121 74.9                                       82  5-methyl                                                                             3'-CH.sub.3                                                                           3"-CF.sub.3 -phenoxy                                                                          71  74.5                                       83  6-methyl                                                                             3'-CH.sub.3                                                                           1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    113 74.9                                       84  6-methyl                                                                             3'-CH.sub.3                                                                           3"-CF.sub.3 -phenoxy                                                                          60  73.2                                       85  5-methyl                                                                             3'-chloro                                                                             1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    116 35.4                                       86  5-methyl                                                                             3'-chloro                                                                             3"-CF.sub.3 -phenoxy                                                                          105 52.4                                       87  6-methyl                                                                             3'-chloro                                                                             1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    96  27.1                                       88  5-methyl                                                                             2',4'-difluoro                                                                        3"-CF.sub.3 -phenoxy                                                                          68  40.4                                       89  5-methyl                                                                             2',4'-difluoro                                                                        2"-chloropyrid-4"-yloxy                                                                       146 58.8                                       90  6-methyl                                                                             2',4'-difluoro                                                                        1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    78  56.4                                       91  6-methyl                                                                             2',4'-difluoro                                                                        3"-CF.sub.3 -phenoxy                                                                          64  65.3                                       92  6-methyl                                                                             2',4'-difluoro                                                                        2"-chloropyrid-4"-yloxy                                                                       162 31.7                                       93  5-methyl                                                                             4'-CF.sub.3                                                                           2"-chloropyrid-4"-yloxy                                                                       99  44.1                                       94  5,6-dimethyl                                                                         4'-CF.sub.3                                                                           1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    136 13.2                                       95  5,6-dimethyl                                                                         4'-CF.sub.3                                                                           3"-CF.sub.3 -phenoxy                                                                          73  65.6                                       96  5,6-dimethyl                                                                         3'-CF.sub.3                                                                           1"-CH.sub.3 -3"-CF.sub.3 -pyrazol-5"-yloxy                                                    132 30.3                                       97  5,6-dimethyl                                                                         3'-CF.sub.3                                                                           3"-CF.sub.3 -phenoxy                                                                          105 67.5                                       __________________________________________________________________________

Example 98 Herbicidal activity

To evaluate their herbicidal activity, compounds according to the invention are tested using a representative range of plants:

    ______________________________________                                         TRZAS            Triticum aestivum                                             HORVW            Hordeum vulgare                                               GOSHI            Gossypium hirsutum                                            HELAN            Helianthus annuus                                             ORYSA            Oryza sativa                                                  GLXMA            Glycine max                                                   BEAVA            Beta vulgaris                                                 ZEAMX            Zea mays                                                      ALOMY            Alopecurus myosuroides                                        AVEFA            Avena fatua                                                   ECHCG            Echinocloa crus-galli                                         SETVI            Setaria viridis                                               GALAP            Galium aparine                                                STEME            Stellaria media                                               CHEAL            Chenopodium album                                             VERPE            Veronica persica                                              LAMPU            Lamium purpureum                                              VIOAR            Viola arvensis                                                SIDSP            Sida spinosa                                                  AMBAR            Ambrosia artemisifolia                                        ABUTH            Abutilon theophrasti                                          IPOPU            Ipomoea purpurea                                              SINAL            Sinapis alba                                                  AMARE            Amaranthus retroflexus                                        ______________________________________                                    

The tests fall into two categories, pre-emergence and post-emergence. The pre-emergence tests involve spraying a liquid formulation of the compound onto the soil in which the seeds of the plant species mentioned above had recently be sown. The post-emergence tests involve spraying seedlings of the above species with a such a formulation.

The soil used in the tests is a prepared horticultural loam. The formulations used in the test are prepared from solutions of the test compounds in acetone containing 0.4% by weight of an alkylphenyl/ethylene oxide condensate surfactant available under the trade mark TRITON X 155. The acetone solutions are diluted with water and the resulting formulations at dosage levels corresponding to 1000 g or 300 g of active material per hectare in a volume equivalent to 400 liters per hectare. In the pre-emergence tests untreated sown soil and in the post-emergence tests untreated soil bearing untreated seedling plants are used as controls.

The herbicidal effects of the test compounds are assessed visually twenty days after spraying the foliage and the soil (in the case of examples 13-16 thirteen days after treatment) and are recorded on a 0-9 scale. A rating 0 indicates growth as untreated control, a rating 9 indicates death. An increase of 1 unit on the linear scale approximates to a 10% increase in the level of effect. An asterisk indicates that the specified plant species was not treated in the test.

The results of the test are set out in the table shown below in which the compounds are identified by reference to the preceding examples. An asterisk indicates that the specified plant species was not treated in the test.

                                                                                      -    T H G H O G B Z A A E S G S C V L V S A A I S A                               R O O E R L E E L V C E A T H E A I I M B P I M                                 Z R S L Y X A A O E H T L E E R M O D  U O N                                 Ex. dose appl. A V H A S M V M M F C V A M A P  A S B T P A A                   No g/ha time W W I N A  A   A G I P  L E P R P A H U L R                                A  X Y     E   U   R    E                                               13 1000 pre * * * * 0 0 4 2 * 2 4 * * * * * * * * * * * 5 *                       post * * * * 2 5 8 4 * 2 5 * * * * * * * * * * * 8 *                          14 1000 pre * * * * 3 4 9 9 * 6 8 * * * * * * * * * * * 8 *                       post * * * * 4 6 9 6 * 6 7 * * * * * * * * * * * 8 *                          15 1000 pre * * * * 0 2 8 2 * 2 5 * * * * * * * * * * * 6 *                       post * * * * 2 6 9 5 * 2 7 * * * * * * * * * * * 6 *                          16 1000 pre * * * * 0 0 2 0 * 0 2 * * * * * * * * * * * 2 *                       post * * * * 0 2 7 4 * 2 2 * * * * * * * * * * * 5 *                          21 300 pre 1 0 0 0 * * * 0 0 * * 0 0 0 * 0 * 0 * * * 0 * *                        post 0 0 1 1 * * * 1 0 * * 0 0 0 * 0 * 0 * * * 0 * *                          22 300 pre 0 0 0 0 * * * 0 0 * * 1 0 0 * 0 * 0 * * * 0 * *                        post 0 0 1 2 * * * 2 0 * * 0 0 0 * 1 * 1 * * * 1 * *                          23 300 pre 1 0 * 1 * * * 1 * * * 0 2 0 0 0 * * * * 0 0 * 0                        post 1 2 * 3 * * * 2 * * * 0 2 4 0 4 * * * * 4 1 * 5                          24 300 pre 0 0 * 0 * * * 0 * * * 0 0 0 0 0 * * * * 0 0 * 0                        post 3 2 * 3 * * * 3 * * * 1 1 2 0 3 * * * * 3 2 * 4                          25 300 pre 0 3 0 0 * * * 3 5 * 6 9 2 7 * 9 8 8 4 4 4 2 * 9                        post 3 3 4 5 * * * 4 5 * 4 6 5 4 * 6 * 6 6 5 4 4 * 6                          26 300 pre 0 1 * 0 * * * 0 * * * 8 0 7 8 8 * * * * 0 0 * 9                        post 4 3 * 4 * * * 3 * * * 3 3 5 6 8 * * * * 5 4 * 7                          27 300 pre 4 6 3 3 * * * 4 9 * 8 9 6 9 * 9 9 8 8 8 6 6 * 9                        post 4 5 6 6 * * * 4 6 * 6 7 5 6 * 6 * 7 8 5 6 6 * 5                          28 300 pre 1 4 2 0 * 3 * 1 8 * 5 9 7 9 * 9 9 8 * * 8 5 * 9                        post 3 5 8 5 * 5 * 8 7 * 4 7 6 7 * 9 7 8 * * 8 6 * 7                          29 300 pre 1 0 0 0 * 0 * 0 3 * 2 8 1 6 * 8 3 8 * * 3 1 * 9                        post 2 2 5 4 * 3 * 3 3 * 2 4 4 5 * 9 5 7 * * 4 5 * 5                          30 300 pre 2 0 0 0 * 2 * 0 0 * 0 0 0 0 * 0 0 0 * * 0 5 * 0                        post 0 0 0 0 * 0 * 0 0 * 0 2 0 0 * 0 0 0 * * 0 1 * 0                          74 300 pre 0 0 0 0 * * * 0 0 * 0 0 0 0 6 0 0 0 0 * 0 0 * 6                        post 0 0 2 0 * * * 0 0 * 0 1 0 0 0 7 0 0 1 * 0 2 * 1                          75 300 pre 3 4 2 1 * * * 2 8 * 6 9 2 9 * 9 9 9 9 * 5 3 * 9                        post 4 5 6 6 * * * 4 7 * 7 6 8 7 * 9 7 8 6 * 6 4 * 6                          76 300 pre 1 3 0 0 * * * 0 8 * * 9 5 9 8 9 8 * 6 * 5 3 * 9                        post 3 3 5 5 * * * 4 4 * * 6 6 8 9 9 8 * 6 * 6 4 * 6                          77 300 pre 3 5 6 3 * 5 * 4 9 * 8 9 8 9 * 9 9 8 * * 8 9 * 9                        post 4 5 8 8 * 8 * 5 7 * 6 8 7 8 * 9 8 9 * * 8 7 * 8                          78 300 pre 3 6 6 2 * 3 * 3 9 * 8 9 8 9 * 9 8 8 * * 9 9 * 9                        post 4 5 8 8 * 8 * 5 6 * 7 9 7 8 * 9 8 8 * * 8 8 * 7                          79 300 pre 4 5 8 3 * 4 * 3 8 * 8 9 8 9 * 9 8 8 * * 9 9 * 9                        post 4 5 8 6 * 6 * 6 8 * 5 8 7 8 * 9 8 8 * * 8 8 * 8                          80 300 pre 4 7 8 3 * 5 * 4 8 * 8 9 8 9 * 9 9 8 * * 9 9 * 9                        post 4 6 9 8 * 8 * 6 7 * 6 8 7 8 * 8 8 8 * * 8 8 * 8                          81 300 pre 0 3 0 0 * 0 * 0 6 * 4 9 0 6 * 9 8 7 * * 2 4 * 8                        post 2 3 4 4 * 5 * 3 3 * 2 8 3 4 * 9 7 5 * * 4 5 * 5                          82 300 pre 0 2 0 0 * 0 * 2 7 * 5 9 1 5 * 9 6 8 * * 4 4 * 9                        post 3 3 4 4 * 4 * 4 4 * 3 4 4 4 * 9 5 7 * * 4 5 * 7                          83 300 pre 0 0 0 0 * 0 * 0 3 * 4 7 1 2 * 8 3 7 * * 1 2 * 9                        post 0 2 4 4 * 3 * 2 3 * 3 4 3 3 * 9 4 5 * * 2 4 * 5                          84 300 pre 0 0 0 0 * 0 * 0 0 * 1 0 0 0 * 0 0 2 * * 0 0 * 0                        post 0 2 0 2 * 1 * 1 1 * 0 1 2 2 * 3 1 5 * * 1 3 * 4                          85 300 pre 1 3 2 0 * 0 * 2 8 * 6 9 6 9 * 8 8 8 * * 5 5 * 9                        post 2 4 5 4 * 5 * 3 5 * 4 5 6 4 * 9 8 7 * * 5 4 * 5                          86 300 pre 2 3 2 0 * 1 * 3 8 * 7 9 3 8 * 9 7 8 * * 5 4 * 9                        post 3 4 8 4 * 5 * 5 5 * 6 7 6 5 * 9 7 8 * * 4 5 * 6                          87 300 pre * * * * * * * * * * * * * * * * * * * * * * * *                        post * * * * * * * * * * * * * * * * * * * * * * * *                          88 300 pre 0 0 0 0 * 0 * 0 0 * 0 0 0 0 * 2 2 4 * * 0 0 * 4                        post 1 1 2 3 * 2 * 1 1 * 2 2 3 4 * 5 3 5 * * 2 6 * 4                          89 300 pre 1 3 2 1 * 5 * 5 5 * 6 8 3 9 * 9 8 9 * * 7 9 * 9                        post 4 4 6 5 * 5 * 5 5 * 6 7 4 5 * 9 6 8 * * 6 7 * 6                          90 300 pre 3 4 3 2 * 3 * 5 8 * 7 9 4 9 * 9 9 9 * * 9 7 * 9                        post 4 5 5 5 * 6 * 5 5 * 6 7 5 6 * 9 6 8 * * 5 7 * 6                          91 300 pre 0 0 0 0 * 0 * 0 3 * 0 9 1 7 * 8 4 8 * * 2 3 * 9                        post 2 2 5 4 * 3 * 3 3 * 3 3 4 4 * 9 5 8 * * 4 6 * 5                          92 300 pre 0 0 1 0 * 0 * 2 2 * 0 8 0 7 * 7 3 8 * * 2 4 * 8                        post 0 1 4 3 * 2 * 2 3 * 2 4 3 5 * 6 4 8 * * 4 6 * 6                          93 300 pre 4 5 7 2 * 3 * 5 8 * 7 9 5 9 * 9 9 9 * * 9 9 * 9                        post 5 5 6 5 * 5 * 6 6 * 7 7 6 6 * 9 6 8 * * 6 8 * 7                          94 300 pre 3 3 5 4 * 3 * 3 8 * 6 9 5 9 * 9 9 9 * * 9 9 * 9                        post 2 4 7 5 * 5 * 3 5 * 5 6 5 5 * 9 6 8 * * 6 9 * 6                          95 300 post 2 5 3 2 * 3 * 3 7 * 6 9 4 9 * 9 6 9 * * 7 6 * 8                       post 2 4 6 5 * 5 * 4 5 * 5 7 5 6 * 8 6 8 * * 5 9 * 6                          96 300 pre 0 0 2 2 * 0 * 2 1 * 0 8 0 4 * 7 0 8 * * 0 5 * 8                        post 1 1 3 4 * 2 * 1 2 * 2 2 4 4 * 7 4 7 * * 4 5 * 4                          97 300 pre 0 0 0 0 * 3 * 0 0 * 0 3 0 0 * 0 0 3 * * 0 3 * 5                        post 0 1 3 2 * 2 * 1 0 * 1 2 3 3 * 4 3 5 * * 2 5 * 5                    

We claim:
 1. A herbicidal composition which comprises a carrier and/or a surface-active agent and as an active ingredient one or more compound of the formula I ##STR25## wherein A represents a substituted phenyl or naphthyl group, or an optionally substituted 5- or 6- membered nitrogen containing heteroaromatic group selected from the group consisting of pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, isoxazolyl, isothiazolyl, trizinyl and difluorobenzodioxolyl groups;m represents an integer from 0 to 5; n represents an integer from 0 to 2; R¹ (or each R¹) independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkoxyalkoxy, alkoxyalkyl, dialkoxyalkyl, alkylthio, amino, alkylamino, dialkylamino, alkoxyamino or formamidino group; R² (or each R²) independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl group or a nitro, cyano, haloalkyl, haloalkoxy, haloalkylthio or SF₅ group;wherein any of the above mentioned moieties comprising an alkyl, alkenyl or alkinyl group, contain 1 to 12 carbon atoms; any alkyl portion of a haloalkyl, haloalkoxy, alkylthio, haloalkylthio or alkoxy group has from 1 to 4 carbon atoms; and the number of carbon atoms in the alkoxyalkyl, alkoxyalkoxy or dialkoxyalkyl groups is less than 6; and wherein any moiety defined above as comprising an optionally substituted alkyl group, including alkyl parts of haloalkyl, alkoxy, alkylthio, haloalkoxy, alkylamino and dialkylamino groups, may be substituted by phenyl, halogen atoms, nitro, cyano, hydroxyl, C₁₋₄ -alkoxy, C₁₋₄ -haloalkoxy and C₁₋₄ -alkoxycarbonyl groups; and any moiety defined above as comprising a substituted phenyl or naphthyl group or an optionally substituted 5- or 6- membered nitrogen containing heteroaromatic group selected from the group consisting of pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, isoxazolyl, isothiazolyl and triazinyl groups, may be substituted by 1 to 5 substituents selected from halogen atoms, and nitro, cyano, amino, hydroxyl, C₁₋₄ -alkyl, C₁₋₄ -alkoxy, C₁₋₄ -haloalkyl, C₁₋₄ haloalkoxy, C₁₋₄ haloalkylthio and halosulfanyl groups; X represents an oxygen or sulphur atom; and Z represents a nitrogen atom.
 2. A herbicidal composition as claimed in claim 1 wherein A represents a phenyl, pyridyl or pyrazolyl group being substituted by one or more of the same or different substituents selected from halogen atoms, alkyl groups, alkoxy groups, haloalkyl groups, haloalkoxy groups, haloalkylthio groups and SF₅ groups.
 3. A herbicidal composition as claimed in claim 2 wherein A has a substituent in the meta-position relative to the point of attachment.
 4. A herbicidal composition as claimed in claim 3 wherein A is meta-substituted by a chlorine atom or a trifluoromethyl group.
 5. A herbicidal composition as claimed in claim 1 wherein X is oxygen.
 6. A herbicidal composition as claimed in claim 1 comprising as an active ingredient one or more compound of formula I selected from the group consisting of:2-(2',4'-difluorophenyl)-6methyl-4-(1"methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine 2-(2',4'-difluorophenyl)-6-methyl-4-(3"-trifluoromethylphenoxy)pyrimidine, 2-(3'-chlorophenyl)-5-methyl-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine, 2-(3'-chlorophenyl)-5-methyl-4-(3"-trifluoromethylphenoxy)pyrimidine, 2-(4'-fluorophenyl)-6-methyl-4-(3"-trifluoromethylphenoxy)pyrimidine, 2-(4'-fluorophenyl)-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)-5-methylpyrimidine, 4-(2"-chloropyrid-4"-yloxy)-2-(2',4'-difluorophenyl)-5-methylpyrimidine, 4-(2"-chloropyrid-4"-yloxy)-5,6-dimethyl-2-(4'-trifluoromethoxyphenyl)pyrimidine, 4-(2"-chloropyrid-4"-yloxy)-5,6-dimethyl-2-(4'-trifluoromethylphenyl)pyrimidine, 4-(2"-chloropyrid-4"-yloxy)-5-methyl-2-(4'-trifluoromethylphenyl)pyrimidine 4-(2"-chloropyrid-4"-yloxy)-6-methyl-2-(4'-trifluoromethoxyphenyl)pyrimidine, 4-(2"-chloropyrid-4"-yloxy)-6-methyl-2-(4'-trifluoromethylphenyl)pyrimidine 5,6-dimethyl-2-(4'-trifluoromethoxyphenyl)-2-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine, 5,6-dimethyl-2-(4'-trifluoromethoxyphenyl)-4-(3"-trifluoromethylphenoxy)pyrimidine, 5,6-dimethyl-2-(4'-trifluoromethylphenyl)-4-(3"-trifluoromethylphenoxy)pyrimidine, 5,6-dimethyl-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)-2-(4'-trifluoromethylphenyl)-pyrimidine, 5-methyl-2-(3'-methylphenyl)-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)pyrimidine, 5-methyl-2-(3"-methylphenyl)-4-(3"-trifluoromethlphenoxy)pyrimidine, 5-methyl-2-(4'-trifluoromethoxyphenyl)-2-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)-pyrimidine, 5-methyl-2-(4"-trifluoromethoxyphenyl)-4-(3"-trifluoromethlphenoxy)pyrimidine, 5-methyl-2-(4'-trifluoromethylphenyl)-4-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)-pyrimidine, 5-methyl-4-(3"-trifluoromethylphenoxy)-2-(4'-trifluoromethylphenoxy)pyrimidine 6-methyl-2-(4'-trifluoromethoxyphenyl)-2-(1"-methyl-3"-trifluoromethylpyrazol-5"-yloxy)-pyrimidine, 6-methyl-2-(4'-trifluoromethoxyphenyl)-4-(3"-trifluoromethylphenoxy)pyrimidine, 6-methyl-4-(3"-trifluoromethylphenoxy)-2-(4'-trifluoromethylphenyl)pyrimidine.
 7. A method of combating undesired plant growth at a locus, which comprises treating the locus with an effective amount of one or more compound of the formula I ##STR26## wherein A represents a substituted phenyl or naphthyl group, or an optionally substituted 5- or 6- membered nitrogen containing heteroaromatic group selected from the group consisting of pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, isoxazolyl, isothiazolyl, triazinyl and difluorobenzodioxolyl groups;m represents an integer from 0 to 5; n represents an integer from 0 to 2; R¹ (or each R¹) independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkoxyalkoxy, alkoxyalkyl, dialkoxyalkyl, alkylthio, amino, alkylamino, dialkylamino, alkoxyamino or formamidino group; R² (or each R²) independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl group or a nitro, cyano, haloalkyl, haloalkoxy, haloalkylthio or SF₅ group,wherein any of the above mentioned moieties comprising an alkyl, alkenyl or alkinyl group, contain 1 to 12 carbon atoms; any alkyl portion of haloalkyl, haloalkoxy, alkylthio, haloalkylthio or alkoxy group has from 1 to 4 carbon atoms; and the number of carbon atoms in the alkoxyalkyl, alkoxyalkoxy or dialkoxyalkyl groups is less than 6; and wherein any moiety defined above as comprising an optionally substituted alkyl group, including alkyl parts of haloalkyl, alkoxy, alkylthio, haloalkoxy, alkylamino and dialkylamino groups, may be substituted by phenyl, halogen atoms, nitro, cyano, hydroxyl, C₁₋₄ -alkoxy, C₁₋₄ -haloalkoxy and C₁₋₄ -alkoxycarbonyl groups; and any moiety defined above as comprising a substituted phenyl or naphthyl group or an optionally substituted 5- or 6-membered nitrogen containing heteroaromatic group selected from the group consisting of pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, isoxazolyl, isothiazolyl and triazinyl groups, may be substituted by 1 to 5 substituents selected from halogen atoms, and nitro, cyano, amino, hydroxyl, C₁₋₄ -alkyl, C₁₋₄ -alkoxy, C₁₋₄ -haloalkyl, C₁₋₄ -haloalkoxy, C₁₋₄ -haloalkylthio and halosulfanyl groups; X represents an oxygen or sulphur atom; and Z represents a nitrogen atom. 